JP2000235284A - Matte wet type developer and method for producing highly designed article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wet developer in which toner particles containing a mat pigment are dispersed, and a method for producing a highly designed article in which a mat image is formed on the surface of a printing raw material using the developer. I do. SOLUTION: A wet developer in which copolymer resin particles composed of a copolymer resin composed of two or more monomer units and containing a mat pigment are dispersed in an electrically insulating dispersion medium is used. (1) (i) The difference Δ (δp ¹ −δd) between the SP value δp ¹ of the homopolymer composed only of the first monomer unit of the copolymer resin and the SP value δd of the dispersion medium is 1.0 or more. (Ii) the difference Δ (δp ² −δd) between the SP value δp ² of the homopolymer composed only of the second monomer unit of the copolymer resin and the SP value δd of the dispersion medium is 1.0 or less; iii) Difference Δ (δp ¹ −δp ² ) between δp ¹ and δp ²
And (2) a core portion in which the copolymer resin particles are insoluble in the dispersion medium, and an outer edge surrounding the core portion and dissolving or swelling in the dispersion medium. And consists of parts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet developer used in a printing system utilizing an electrostatic action such as an electrostatic plotter, an electrophotographic system, and an electrostatic gravure printing. In addition, the present invention, high-quality printed goods and furniture, building interior materials,
The present invention also relates to a high-design article with a matte image, which is highly useful for uses such as packaging materials.

More specifically, a wet developer capable of imparting a matte feeling to the surface of a printing medium produced by the above-described electrostatic method, various printing methods and dyeing methods,
The present invention relates to a high-design article provided with a matte feeling by using such a wet developer. Further, the present invention uses an on-demand type printing method such as an electrostatic plotter or an electrophotographic method among printing methods utilizing an electrostatic action, and the surface of various printed materials, in particular, furniture and the like whose design is valued is important. The present invention also relates to a wet developer suitable for imparting a matte feeling to the surface of a building interior material, a soft packaging material and the like.

[0003]

2. Description of the Related Art When an image is output using an on-demand printer such as an electrostatic plotter or an electrophotographic printer, three colors (yellow, magenta, cyan) or four colors (yellow, magenta, cyan) are usually used. , Black) is used to form a color image. Therefore, development of toner colorants used when outputting with an on-demand printer has been mainly performed on yellow, magenta, cyan and black process colors.

[0004] On the other hand, in the case of producing a high-design printed matter using a conventional printing machine such as gravure printing or offset printing, a mat varnish is used as a finishing varnish for suppressing the surface gloss of the printed matter and expressing a calm and high-quality appearance. Such matte varnish finishes are known and are used, for example, in publishing and commercial prints such as high-end design collections and photo books.

[0005] In addition, characters and pictures are printed on the surface of furniture such as a system kitchen, storage furniture, light electrical equipment cabinets, or architectural interior materials such as wallpaper and flooring by using a printing method such as gravure or offset. Artificial patterns,
2. Description of the Related Art Attaching a pattern of a natural object such as a wood grain or a stone grain or other images has been conventionally performed. In order to apply patterns and other images to the surfaces of furniture and building interior materials, images are applied to the surface of various raw materials (preformed or rough molded) selected according to the application using an appropriate system or method. After that, the raw material is subjected to post-processing such as foaming and melamine processing.

[0006] In various printing systems, when a full-color image is formed, various colors are usually expressed using process inks of three colors (yellow, magenta, cyan) or four colors (yellow, magenta, cyan, black). I have. In addition, special colors, such as light beige and light gray, are special inks that are pre-adjusted to specific colors for colors that tend to fluctuate between products when expressed by mixing process inks. To
It is often used without mixing with other color inks.
Furthermore, in order to reduce gloss and express a calm and high-grade feeling using a matte effect (matte effect), clay or calcium carbonate with low lipophilicity is mixed with printing ink or overprinted. ing. In particular, in the case of furniture, building interior materials, and packaging materials, such matting effect is considered to be indispensable as enhancing the commercial value.

[0007] In the recent flow of small lots and many kinds,
Since on-demand printers play a large role, the inventors have not only produced various printed materials using on-demand printers such as electrostatic plotters and electrophotographic printers, but also developed them into furniture and building interior materials. Was. However, there is no system for expressing a matte feeling using an on-demand printer, and therefore, on-demand prints with a short delivery date and a small lot are manufactured for use in furniture, building interior materials, soft packaging materials, high-quality prints, and the like. However, a printed matter having a matte feeling could not be obtained.

[0008]

SUMMARY OF THE INVENTION The present inventors have proposed that if a matte pigment can be converted into a toner, a matte image having a desired pattern can be formed on a surface of a furniture, a building interior material, or a raw material thereof. We thought that it would be possible to form easily and quickly using on-demand printers such as plotters and electrophotographic printers, and to be able to flexibly create articles of various designs. However, in order to convert the mat pigment into a toner, the mat pigment must have excellent dispersibility and chargeability.

The present invention has been accomplished in view of the above situation, and a first object of the present invention is to provide a wet developing method in which toner particles containing a mat pigment and having excellent chargeability are well dispersed. To provide an agent. Further, a second object of the present invention is to provide an image with a matte feeling by using an on-demand type printing method using a wet developer containing such a matte pigment, and to be useful as furniture and building interior materials. It is an object of the present invention to provide a method for manufacturing a highly designed article.

[0010]

In order to achieve the above-mentioned object, the present invention is characterized in that, in the first aspect, resin particles containing a mat pigment are dispersed in an electrically insulating dispersion medium. Provide a matte wet developer.

By using such a matte wet developer of the present invention, various sheet-like or three-dimensional sheets can be formed by an electrostatic plotter, an electrophotographic system, or a printing system utilizing an electrostatic action such as electrostatic gravure printing. An image having a matte feeling can be provided on the surface of a typical printing medium, and a highly designed article can be obtained. In particular, the matte wet developer of the present invention is suitable for an on-demand type printing method such as electrostatic recording and electrostatic transfer among electrostatic printing methods, and can easily and quickly produce an image having a matte feeling. Enables printing.

By using the matte wet developer of the present invention, an image having a matte feeling can be formed by an electrostatic printing method regardless of whether the base material of the printing medium or the ink has gloss. In particular, even when the material of the base cannot be freely selected, such as when attaching a matte image to furniture or architectural interior materials, the matte wet developer of the present invention can be used for matting by an electrostatic method. An image having a feeling can be formed. Further, by providing an image having a matte feeling in a pattern, a printed matter having very excellent design properties can be obtained.

In the present invention, as described in claim 2, the average particle size of the mat pigment is preferably in the range of 0.5 to 20 μm. This is because the matte feeling of the image is expressed by the formation of a matte printing layer on the surface of the image. Causes diffuse reflection of the image, giving the image a matte feeling full of luxury. Therefore, it is preferable that the matte pigment has a particle size that can form minute irregularities so as to cause irregular reflection of light on the surface of the matte print layer, that is, within a range of 0.5 to 20 μm.

In the present invention, as described in claim 3, the resin particles in the matte wet developer are composed of at least two types of monomer units including at least a first monomer unit and a second monomer unit. Resin particles composed of a copolymer resin as described above, wherein the electrically insulating dispersion medium and the copolymer resin are (i) a solubility parameter value δp of a homopolymer composed of only the first monomer unit of the copolymer resin.
The difference Δ (δp ¹ −δd) between ¹ and the solubility parameter value δd of the electrically insulating dispersion medium is 1.0 or more, and (ii) the solubility of a homopolymer composed only of the second monomer unit of the copolymer resin. The difference Δ (δp ² −δ) between the parameter value δp ² and the solubility parameter value δd of the electrically insulating dispersion medium.
d) is 1.0 or less, and (iii) the difference Δ (δ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
p ¹ −δp ² ) is equal to or greater than 0.5, and the copolymer resin particles have a core portion insoluble in the electrically insulating dispersion medium and an electric insulating property surrounding the core portion. It preferably comprises an outer edge portion that dissolves or swells in the dispersion medium.

Here, the SP value (solubility parameter value) δd of the electrically insulating dispersion medium used in the present invention is represented by δ
The difference Δ (δp ¹ −δd) between d and the SP value δp ¹ of the homopolymer composed only of the first monomer unit of the copolymer resin becomes 1.0 or more, and the difference Δd and the second value of the copolymer resin
SP value δ of homopolymer composed only of monomer units
The difference Δ (δp ² −δd) from p ² has a relationship of 1.0 or less. That is, the dispersion medium used in the present invention is:
The affinity for the first monomer unit portion of the copolymer resin is low, while the affinity for the second monomer unit portion of the copolymer resin is high. Moreover, since the difference Δ (δp ¹ −δp ² ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers is 0.5 or more, the affinity of the dispersion medium for the portion of the first monomer unit and the There is considerable variation in the affinity of the dispersion medium for the portion of two monomer units.

Therefore, a solution of a copolymer resin composed of at least a first monomer unit and a second monomer unit,
When the electrically insulating dispersion medium having the SP value characteristic as described above is mixed under the condition that a mat pigment originally having a low affinity for the electrically insulating dispersion medium is present, the first monomer unit of the copolymer resin is obtained. Are repelled by the dispersion medium and adsorbed on the surface of the matte pigment. As a result, the copolymer resin is microscopically aggregated around the matte pigment. Thus, copolymer resin particles including the mat pigment are formed.

The formed copolymer resin particles are composed of a core portion insoluble in the dispersion medium and an outer edge portion surrounding the core portion, which dissolves or swells in the dispersion medium. Here, the core portion is composed of a mat pigment and a portion having a high affinity for the mat pigment in the molecule of the copolymer resin, particularly a portion of the first monomer unit. Further, the outer edge portion is formed of a portion having a high affinity for the electrically insulating dispersion medium in the molecule of the copolymer resin, particularly a portion of the second monomer unit. Since the copolymer resin particles have such a structure, the mat pigment particles are prevented from directly contacting each other, are well dispersed in a dispersion medium, and are unlikely to cause precipitation or macroscopic aggregation. Also, such copolymer resin particles,
It also has moderate chargeability. Accordingly, such a matte wet type developer is preferable because toner particles having a matt feeling and having an appropriate chargeability are dispersed well.

In converting the matte pigment into a toner,
It is important to properly adjust the charge amount of the toner particles, and it is also important to intentionally adjust the polarity of the charge to either positive or negative.

In the present invention, the first monomer unit having a basic group, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate may be used. And a second resin unit derived from at least one monomer selected from the group consisting of ethylene and a copolymer resin at least comprising a mat pigment.

Further, the first monomer unit having a basic group is, as described in claim 5, dimethylaminoethyl acrylate, dimethylacrylamide acrylate, diacetone acrylamide, isopropylacrylamide, dimethylaminoethyl methacrylate, It is preferably a monomer unit derived from at least one monomer selected from the group consisting of methacrylic acid dimethylacrylamide.

By selecting such a monomer unit and adding a metal soap as a charge control agent,
As described in claim 6, the copolymer resin particles in the matte wet developer can be usually positively charged.

In the present invention, as described in claim 7, a first monomer unit having an acidic group, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, It is preferable to include a mat pigment using a copolymer resin composed of at least a second monomer unit derived from at least one monomer selected from the group consisting of ethylene and ethylene.

Further, as described in claim 8, the first monomer unit having an acidic group is a monomer unit derived from at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and vinyl acetate. Preferably, there is.

By selecting such a monomer unit and adding lecithin as a charge control agent,
As described in claim 9, the copolymer resin particles in the matte wet developer can be usually negatively charged.

The method for producing a highly designed article according to the present invention comprises:
As described in claim 10, a first object to prepare a printing medium selected from furniture, architectural interior materials, packaging materials, paper, films, and their webs, and the above-described matte wet developer. And at least a second step of adhering resin particles containing a matte pigment to the surface of the printing medium by performing electrostatic recording or electrostatic transfer using the matte wet developer. is there.

Here, the electrostatic recording and the electrostatic transfer are both on-demand type printing methods, and the electrostatic recording is performed by using an apparatus such as an electrostatic plotter. This is performed using a device such as a printer.
According to the above method, an on-demand type printing method using a wet developer containing matte toner particles,
It is possible to easily and quickly output a matte image on the surface of furniture, a building interior material, or a raw material thereof. No plate making process is required. Therefore, high-design articles useful as furniture and building interior materials can be flexibly manufactured. The high-design article according to the present invention refers to a high-design article having at least one mat printing layer printed on the surface of a printing medium using a matte wet developer.

The above method is particularly suitable for producing furniture, building interior materials, flexible packaging materials, and high-quality printed products. That is, in the first step, a printed body having a pattern formed with color ink or toner is prepared as a raw material, and in the second step, copolymer resin particles containing a mat pigment on the surface of the printed body are provided. Can be produced uniformly or in a pattern to produce a high-designed mat print. In addition, by forming a pattern with glitter ink or toner after mat printing, a printed matter having a higher design can be manufactured.

In the method for producing a highly decorative article,
Further, as described in claim 11, after the second step, it is preferable to perform a post-processing for improving the designability. Examples of such post-processing methods include, for example, an example in which surface coating is performed using a melamine paint or the like. Is to continue foaming,
Performing embossing is also included in the post-processing described here. In addition, laminating treatment of a soft packaging material is also included.

Further, the invention described in claim 12 is:
Furnishings, building interior materials, packaging materials, paper, films, and substrates to be selected from among these materials, having at least one mat printing layer printed using the matte wet developer described above. It is a printed matter characterized by the following.

The printed matter according to the present invention has a mat print layer formed by using a matte wet developer. Therefore, among the electrostatic printing methods, a printed matter having a matte image can be easily and quickly obtained by an on-demand type printing method such as electrostatic recording or electrostatic transfer. Having at least one mat printing layer means that at least one mat printing layer may be formed on the printing medium, and the mat printing layer may be formed on the printing medium side or outside of the mat printing layer. A color print layer or a glitter print layer may be formed. Further, if necessary, a plurality of mat printing layers may be provided in the same or different patterns.

Further, it is preferable that the printed matter is subjected to post-processing after forming the outermost layer as described in claim 13. This is because such post-processing is preferable in terms of design. The post-processing is the same as described above. Further, as described in claim 14, it is preferable that the raw material is a foaming vinyl chloride raw material, and that the subsequent chemical conversion is embossing in terms of design properties and the like.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

(1) Matting wet type developer and method for producing the same The matting wet type developer according to the present invention is obtained by dispersing resin particles containing a mat pigment in an electrically insulating dispersion medium. In the present invention, the resin forming the resin particles is preferably a copolymer resin composed of at least two types of monomer units including a first monomer unit and a second monomer unit.

The matte wet developer of the present invention is obtained, for example, by mixing a solution of the above copolymer resin in a good solvent and an electrically insulating dispersion medium in the presence of a mat pigment such as silica fine particles. It can be produced by granulating resin particles and then removing a good solvent as required.

According to the present invention, the copolymer resin particles containing the mat pigment are precipitated from the varnish or solution of the copolymer resin, and the SP value of the electrically insulating dispersion medium to be dispersed is adjusted, whereby the copolymer resin particles are dispersed. That is, a wet developer excellent in dispersibility of toner particles is provided.

[Solubility Parameter (SP Value)] In general, the SP value is known as an index indicating compatibility or incompatibility between substances. Taking the relationship between resin and solvent as an example,
The degree of solubility of the resin in the solvent can be indicated by the SP value. If the difference between the SP value of the resin and the SP value of the solvent is small, the solubility is high and the solvent becomes easily soluble. On the other hand, if the difference is large, the solubility is low and the solvent becomes insoluble.

As a method for measuring the SP value of a resin, for example, (1) a method based on a dissolution method, that is, a method of estimating from the SP value of a solvent in which a resin is dissolved (H. Burrell, Official
Digest, 27 (369), 726 (1950)), (2) swelling method, that is, for a resin that is difficult to dissolve, a method of estimating from the SP value of a solvent that maximizes the swelling degree (Id.), (3) A) The method of obtaining from the intrinsic viscosity of the resin, that is, the intrinsic viscosity of the resin in the solvent shows the maximum value when the SP value of the resin matches the SP value of the solvent. Therefore, the resin is dissolved in a solvent having various SP values, and the respective intrinsic viscosities are measured.
From the SP value of the solvent that gives the maximum value of the intrinsic viscosity, the SP of the resin
Method for estimating values (H. Ahmed, M, Yassen, J. Coat. Tec
hnol., 50, 86 (1970), WR Song, DW Brownawell,
Polym. Eng. Sci., 10, 222 (1970)), (4) a method of obtaining from a molecular attraction constant, that is, a molecular attraction constant (G) of each functional group or an atomic group constituting a resin molecule, and a molar volume ( V), a method of obtaining SP value = ΣG / V (DA Small, J. Appl. Chem., 3, 71 (1953), KL H
oy, J. Paint Technol., 42, 76 (1970)).

Hereinafter, in the present invention, a value determined by a molecular attraction constant is used as the SP value of the resin. As the SP value of the solvent, Hildebrand-Scatchard solution theory (JH Hildebrand, RL Scott, “The Solbil
ity of Nonelectrolytes '' 3rd Ed., Reinhold Publish
ing cop., New York (1949), G. Scatchard, Chem., Re.
v., 8, 321 (1931)) based on the attractive force between molecules.

[0039]

SP value (δ) = (ΔE _V / ΔV ₁ ) ^1/2 [where ΔE _V : evaporation energy, V ₁ : molecular volume, ΔE
_V / ΔV ₁ : cohesive energy], and in the present invention, KL Hoy, J. Paint Technol., 42, 76 (1
970) at 25 ° C. are used.

The relationship between the SP value of the resin and that of the solvent will be described by taking the case where the resin is dissolved in a solvent as an example. Polystyrene having an SP value of 9.1 is very soluble in tetrahydrofuran having an SP value of 9.1 And SP value is 8.5-
Solvents in the 9.3 range are soluble and have SP values of 7.3.
Does not dissolve in n-hexane. Thus, the state of the resin in the solvent can be estimated by looking at the difference between the SP values of the resin and the solvent.

After dissolving the resin in a relatively dilute state in a good solvent, adding the solution to a poor solvent and removing the good solvent, resin particles can be precipitated. However, it can be considered that in a good solvent, a resin that was present in a monomolecular state and in a state where molecular chains were elongated, but in a poor solvent, molecular chains shrank and became particles, which led to precipitation. . Therefore, a solvent having a difference in SP value such that the resin swells is used as the poor solvent.
The state of the resin particles in the solvent differs depending on whether a solvent in which the P value is large and the resin is completely insoluble is used. Generally, as the weight average molecular weight of the resin increases, the particle size of the formed resin particles increases.

[Copolymer Resin] In the present invention, the resin is used to enhance the dispersibility of a mat pigment such as silica fine particles.
It is preferable that the copolymer resin is composed of two or more types of monomer units including a monomer unit.

As such a copolymer resin, for example,
Styrene-butadiene copolymer resin, styrene-isoprene copolymer resin, styrene-acrylonitrile copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-methacrylate copolymer resin , Ethylene-
Thermoplastic resins such as ethyl acrylate copolymer resin, vinyl acetate-methyl methacrylate copolymer resin, acrylic acid-methyl methacrylate copolymer resin, and vinyl chloride-vinyl acetate copolymer resin can be used. The melt flow rate (MFR) of the copolymer resin specified by ASTM D-1238 is usually 1 to 400 dg / min,
Preferably it is 2-150 dg / min. This MFR
When the value range is converted into a weight average molecular weight, it is 1 to 400 d.
g / min corresponds to a weight average molecular weight of about 60,000 to 250,000, and 2 to 150 dg / min corresponds to a weight average molecular weight of about 75,000 to 200,000.

The copolymer resin used in the present invention is preferably composed of two or more types of monomer units, has a low affinity for an electrically insulating dispersion medium, and therefore has a portion insoluble in the dispersion medium. A first monomer unit that is considered to form and a second monomer unit that has a high affinity for the electrically insulating dispersion medium and is therefore considered to form a portion that dissolves or swells in the dispersion medium. Contains. The weight ratio of the first monomer unit to the second monomer unit is 95/5 to 5/95, preferably 85/1.
5 to 15/85.

As the first monomer unit, for example, (meth) acrylic acid, methyl (meth) acrylate, (meth)
(Meth) acrylates having short-chain methylenes such as ethyl acrylate, butyl (meth) acrylate;
Nitrogen-containing acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; acrylamide, isopropylacrylamide, methylenebisacrylamide, N-allylacrylamide, N-diacetoneacrylamide, N, N-
Acrylamide derivatives such as dimethylacrylamide; derived from other monomers such as (meth) acrylic acid-2-hydroxyethyl ester, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, methylstyrene, and vinyl acetate A monomer unit can be exemplified. In particular, those derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, methylstyrene, and vinyl acetate are preferred as the first monomer unit.

As the second monomer unit effective for controlling the solubility and dispersibility in a solvent, a vinyl monomer having a long-chain methylene as a side chain, more specifically (meth)
Monomer units derived from (meth) acrylates having long-chain methylene, such as 2-ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and ethylene, isoprene, butadiene, and propylene And a monomer unit derived from a vinyl monomer. In particular, 2-ethylhexyl (meth) acrylate or one derived from ethylene is preferred as the second monomer unit.

In the case of a copolymer resin having three or more monomer units, the one having the largest difference from the SP value of the dispersion medium is specified as the first monomer unit, and the difference from the SP value of the dispersion medium is determined. The smallest one may be specified as the second monomer unit, and its weight ratio may be the same as that of the above-mentioned two-component copolymer resin. Further, if the third monomer component has the same SP value as one of the first and second monomer units forming the insoluble portion or the soluble portion in relation to the SP value of the dispersion medium, such a case is possible. It may be considered a component equivalent to a monomer unit having an approximate SP value.

[Matte pigment] Examples of pigments having a matte feeling include clay minerals such as kaolinite, halosite, muscovite, and talc; and synthetic achromatic pigments such as anhydrous silica, anhydrous alumina, calcium carbonate, magnesium carbonate, and barium carbonate. Among them, a synthetic silica called white carbon (refractive index: 1.45) is preferable as a pigment having good surface reflection characteristics and excellent mat characteristics without impairing the transparency.

Even when the same pigment is used, the matte feeling of the material greatly depends on the particle size of the pigment fine particles.
0.5 to 20 μm is appropriate, and especially 0.5 to 10 μm.
It is preferable that the average particle size is 1 μm, especially 1 to 5 μm.

In the present invention, usually, a mat pigment powder having an average particle size of 0.5 to 10 μm in a secondary aggregation state is used. The mat pigment can be included in the copolymer resin particles in an amount of up to 80% by weight, preferably up to 75% by weight. The matte wet developer of the present invention hardly causes problems such as macroscopic aggregation even when a large amount of copolymer resin particles are contained, so that the content of the matte pigment can be increased.

[Relationship between Matte Pigment and Copolymer Resin] The matte feeling of an image is expressed by forming a matte layer on the image surface. The formed mat layer causes diffuse reflection of light by forming minute surface irregularities on the coating film surface,
Gives a high-quality matte feeling to the image. Therefore, it is necessary for the mat pigment to have a particle size that can form minute irregularities so as to cause irregular reflection of light on the surface of the mat layer, and the above-described 0.5 to 20 μm is appropriate. It is preferably from 10 to 10 µm, and particularly preferably from 1 to 5 µm.

When the difference between the refractive index of the resin forming the coating film and the refractive index of the matte pigment is large, light scattering at the interface between the resin and the matt paint becomes large, and the intensity of incident light and reflected light is remarkable. As a result, the image density of the background image is significantly reduced, and the background image is concealed, which is not preferable.

That is, by reducing the difference between the refractive index of the resin used for the mat toner and the refractive index of the mat pigment and controlling the particle size, light scattering inside the mat layer is suppressed and the underlying image is concealed. Without this, it is possible to suppress the "teri" on the image surface. The refractive index of a general resin is about 1.4 to 1.6, and it is preferable that the refractive index of the mat pigment is also about this.

[Charge Control Agent] In the present invention, the charge amount and / or the polarity of the charge of the copolymer resin particles as the toner particles may be controlled by using a charge control agent.
Examples of the charge control agent include metal salts of dialkyl sulfosuccinates such as cobalt dialkyl sulfosuccinate, manganese dialkyl sulfosuccinate, zirconium dialkyl sulfosuccinate, yttrium dialkyl sulfosuccinate, nickel dialkyl sulfosuccinate; manganese naphthenate, calcium naphthenate, naphthenate Zirconium, cobalt naphthenate, iron naphthenate, lead naphthenate, nickel naphthenate, chromium naphthenate, zinc naphthenate, magnesium naphthenate, manganese octylate, calcium octylate, zirconium octylate,
Iron octylate, lead octylate, cobalt octylate, chromium octylate, zinc octylate, magnesium octylate, manganese dodecylate, calcium dodecylate, zirconium dodecylate, iron dodecylate, lead dodecylate,
Metal soaps such as cobalt dodecylate, chromium dodecylate, zinc dodecylate and magnesium dodecylate; metal salts of alkylbenzenesulfonic acids such as calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate and barium dodecylbenzenesulfonate; lecithin, seharin and the like Phospholipids; organic amines such as n-decylamine and the like can be used.

In converting the matte pigment into a toner,
It is important to appropriately adjust the charge amount of the toner particles, but more importantly, it is more important to intentionally adjust the polarity of the charge to either positive or negative. The charge polarity of the mat toner particles can be adjusted by a combination of a specific copolymer resin and a specific charge control agent.

That is, a first monomer unit having a basic group, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and
Including a mat pigment using a copolymer resin composed of at least a second monomer unit derived from at least one monomer selected from the group consisting of stearyl methacrylate, and adding a metal soap as a charge control agent Thereby, the copolymer resin particles in the matte wet developer can usually be positively charged.

Here, the first monomer unit having a basic group includes dimethylaminoethyl acrylate, dimethylacrylamide acrylate, diacetone acrylamide,
The monomer unit is preferably a monomer unit derived from at least one monomer selected from the group consisting of isopropylacrylamide, dimethylaminoethyl methacrylate, and dimethylacrylamide methacrylate. As the metal soap, a metal salt of naphthenic acid or octylic acid, particularly, zirconium naphthenate or zirconium octylate can be preferably used.

The first monomer unit having an acidic group and at least one monomer selected from the group consisting of 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate Including a mat pigment using a copolymer resin composed of at least a second monomer unit to be derived, and adding lecithin as a charge control agent, copolymer resin particles in a matte wet developer, Usually, it can be negatively charged.

Here, the first monomer unit having an acidic group is preferably a monomer unit derived from at least one monomer selected from the group consisting of acrylic acid and methacrylic acid.

[0060] Lecithin is a phospholipid represented by the following formula (1).

[0061]

Embedded image In the formula (1), R ¹ CO and R ² CO each represent a saturated or unsaturated acyl group, and the number of carbon atoms is not particularly limited.

Since lecithin has both a hydrophobic fatty acid glyceride group and a hydrophilic phosphate group or ethanolamino group in its molecule, it has a zwitterionic surfactant activity. . Lecithin has an acid value of about 2
At 0, it is a waxy substance, and at an acid value of about 30, it is a viscous liquid. Lecithin is insoluble in water, but swells with water. As lecithin, for example, soybean lecithin and egg yolk lecithin can be used. The constituent fatty acids of soy lecithin are palmitic acid 11.7%, stearic acid 4%, palmitooleic acid 8.6%, oleic acid 9.8%, linoleic acid 55%, and linolenic acid 4%. And an acid having 20 to 22 carbon atoms is 5.5%.

The charge control agent may be added in a minimum amount that exhibits a charge control effect. Usually, the charge control agent is added to a wet developer at a ratio of 0.01 to 50% by weight. The charge control agent exhibits a charge control effect when added at any stage after the production process or after the solvent is removed, but is preferably added in the production process before the granulation process, and the Alternatively, the varnish and the electrically insulating dispersion medium are mixed in the presence of the matte pigment and the charge control agent.

[Additives] If necessary, other additives such as a dispersant and a fixing agent may be added to the wet developer of the present invention. The copolymer resin in the present invention itself has excellent affinity with the dispersion medium, so a dispersant is not necessarily required, but dispersibility in a good solvent is improved by allowing the dispersant to be present in the granulation step described below. In addition, since the entanglement of molecular chains during granulation is controlled, the particle size of the toner particles can be reduced to a submicron unit,
In addition, the particle size distribution can be narrowed.

As such a dispersant, for example, a polymer dispersant such as a polyhydroxycarboxylic acid ester can be used. The polyhydroxycarboxylic acid ester is a polymer of an ester derivative of hydroxycarboxylic acid represented by the following formula.

[0066]

HO-X-COOH wherein X is a divalent saturated or unsaturated aliphatic hydrocarbon having 12 or more carbon atoms, and at least 4 There are carbon atoms. Preferred ester derivatives of hydroxycarboxylic acid include, for example, hydroxycarboxylic acid alkyl esters such as 12-hydroxystearic acid methyl ester and 12-hydroxystearic acid ethyl ester;
Hydroxycarboxylic acid metal salts such as lithium-hydroxycarboxylate and aluminum 12-hydroxycarboxylate; hydroxycarboxylic acid amide; hardened castor oil and the like.

The polyhydroxycarboxylic acid ester is a light gray-brown wax-like substance obtained by polymerizing a hydroxycarboxylic acid ester by partially saponifying it in the presence of a small amount of amines or a catalyst. It contains various forms such as those esterified between molecules and those esterified within a molecule.

The polyhydroxycarboxylic acid ester is preferably a 3- to 10-mer of hydroxycarboxylic acid ester. If the degree of polymerization of the polyhydroxycarboxylic acid ester is smaller than 3 or larger than 10, there is no compatibility with a dispersion medium such as n-hexane and the effect as a dispersant cannot be obtained. The addition amount of the polyhydroxycarboxylic acid ester is not particularly limited, but is usually 0.01 to
It is 200% by weight. The polyhydroxycarboxylic acid ester may be added at any point during the production process before the granulation process.

As the fixing agent, for example, various resins soluble in a dispersion medium such as n-hexane can be used. More specifically, modified or unmodified alkyd resins, ordinary alkyl resins, synthetic resins, Rubber, polyalkylene oxide, polyvinyl acetal (for example, polyvinyl butyral),
Examples thereof include a vinyl acetate resin.

[Solvent] Copolymer resin particles can be granulated by utilizing the difference in SP value between the solution capable of dissolving or swelling the copolymer resin and the electrically insulating dispersion medium. The solvent may not completely dissolve the copolymer resin,
It is capable of dissolving and swelling the copolymer resin at room temperature (25 ° C.), or it can satisfactorily disperse a partial homopolymer chain existing in the copolymer resin even if it is in an insoluble state. Must be something. The solvent is
It must be insoluble or hardly soluble with respect to the mat pigment constituting the core of the copolymer resin particles.

In order to have good solubility in the copolymer resin, the SP value of the solvent must be equal to the SP value δ of the homopolymer composed only of the first monomer unit in the copolymer resin molecule.
p ^1, and, must approximate to either the SP value .delta.p ² homopolymers made up of only the second monomer units in the copolymer resin molecules, approximation to both .delta.p ¹ and .delta.p ² Preferably.

For example, in the case of a styrene-isoprene copolymer resin, the polystyrene (first monomer unit) SP
Value of 9.1, S of polyisoprene (second monomer unit)
The P value is 8.15. Therefore, toluene (SP value:
8.9) or cyclohexane (SP value: 8.2).

As a solvent for dissolving the copolymer resin, for example, cyclohexane (SP value: 8.2), cellosolve acetate (SP value: 9.4), toluene (SP value: 8.9), tetrahydrofuran (SP value: 9.1) ), Methyl ethyl ketone (SP value 9.5), cyclohexanone (SP value 10.
4), acetone (SP value 9.6), dioxane (SP value 10.1), ethyl cellosolve (SP value 10.7), cyclohexanol (SP value 11.4), methyl cellosolve (SP value 11.7) , Isopropyl alcohol (SP
Value 11.4), ethanol (SP value 12.8), methanol (SP value 14.5) and the like.

[Electrically Insulating Dispersion Medium] As the electrically insulating dispersion medium, one having an electric resistance of 10 ¹⁰ Ω · cm or more is usually used. In the present invention, the following SP
It is necessary to use an electrically insulating dispersion medium having value characteristics. (I) an SP value δp ¹ of a homopolymer composed of only the first monomer unit as a part of the copolymer resin molecule,
The difference Δ (δp ¹ −δd) from the SP value δd of the dispersion medium is
1.0 or more. (Ii) SP value δp of a homopolymer composed of only the second monomer unit as a part of the copolymer resin molecule
² and the difference Δ (δp ² −δd) between the SP value δd of the dispersion medium
Is 1.0 or less. (Iii) The difference Δ (δp ¹ −δp ² ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers is 0.5 or more.

For example, by mixing a solution of a styrene-isoprene copolymer resin with n-hexane in the presence of a mat pigment, particles of the styrene-isoprene copolymer resin including the mat pigment can be precipitated. In this case, the SP value δp ^{1 of} polystyrene (first monomer unit) is 9.1, and polyisoprene (second monomer unit)
Has an SP value δp ² of 8.15 and an SP value δd of n-hexane (dispersion medium) of 7.3, so that the above condition is satisfied as shown in the following calculation formula.

[0076]

## EQU2 ## δp ¹ −δd = 9.1-7.3 = 1.8∴Δ (δp ¹ −δd) ≧ 1 δp ² −δd = 8.15−7.3 = 0.85∴Δ (δp ^2- δd) ≦ 1 δp ¹ −δp ² = 9.1-8.15 = 0.95５Δ (δp ¹ −δp ² ) ≧ 0.5 And the particles of the styrene-isoprene copolymer resin are dispersed in a dispersion medium. In n-hexane, a portion derived from an isoprene unit forms an outer edge portion in a dissolved or swollen state, and a portion derived from a styrene unit is adsorbed on the surface of a mat pigment, and an insoluble core is formed together with the mat pigment. It can be considered to take a shape in which a part is formed.

Here, the homopolymers which can serve as indices when specifying the SP value of the homopolymer composed of only the first monomer unit or the second monomer unit of the copolymer resin and the SP value of each homopolymer are listed as follows. become that way. Polyethylene (8.1), polybutadiene (8.
4), polyisoprene (8.15), polyisobutylene (7.7), polylauryl methacrylate (8.2),
Polystearyl methacrylate (8.2), polyisobonyl methacrylate (8.2), poly-t-butyl methacrylate (8.2), polystyrene (9.1), polyethyl methacrylate (9.1), polymethyl methacrylate (9.3), polymethyl acrylate (9.
7), polyethyl acrylate (9.2), polyacrylonitrile (12.8).

The following is a list of usable electrically insulating dispersion media and SP values of the respective dispersion media. n-hexane (7.3), n-heptane (7.5), n-octane (7.5), nonane (7.6), decane (7.7),
Dodecane (7.9), cyclohexane (8.2), perchlorethylene (9.3), trichloroethane (9.
9). An electrically insulating solvent having an SP value of 7.0 to 7.3 supplied from Exxon under the trade name of Isopar, more specifically Isopar G, Isopar H, Isopar L, Isopar C, Isopar E, Isopar M or the like may be used as the dispersion medium.

Preferred combinations of the copolymer resin and the electrically insulating dispersion medium include the following combinations.

First, in the case of using n-hexane (δd = 7.3) as a dispersion medium, preferred copolymer resins are listed, and a homopolymer SP composed only of the first monomer unit of the copolymer resin is listed. Difference Δ (δp ¹ −δd) between the value δp ¹ and the SP value δd of the dispersion medium, and the difference between the SP value δp ^{2 of the} homopolymer composed of only the second monomer unit of the copolymer resin and the SP value δd of the dispersion medium. Δ (δp ² −δ
d) and the difference Δ (δp ¹ −δp ² ) between δp ¹ and δp ² is also described. However, the numerical value in parentheses is the SP value of the homopolymer composed only of the monomer unit. Ethylene (8.1) -vinyl acetate (9.4) copolymer resin, Δ (δp ¹ −δd) = 2.1, Δ (δp ² −δd) =
0.8, Δ (δp ¹ −δp ² ) = 1.3 Ethylene (8.1) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.4, Δ (δp ² −δ
d) = 0.8, Δ (δp ¹ −δp ² ) = 1.6 Ethylene (8.1) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.9, Δ (Δp ² −δ
d) = 0.8, Δ (δp ¹ −δp ² ) = 1.1 Styrene (9.1) -isoprene (8.15) copolymer resin, Δ (δp ¹ −δd) = 1.8, Δ ( δp ² −δd) =
0.9, Δ (δp ¹ −δp ² ) = 0.9 Lauryl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) = 2.
0, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 1.1 lauryl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) = 1.
8, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 0.9 lauryl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ -δd) = 2.
4, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 1.5 lauryl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
9, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 1.0 lauryl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) = 1.
7, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 0.8 stearyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
2.0, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp
² ) = 1.1 Stearyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.8, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp
² ) = 0.9 Stearyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.
4, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 1.5 Stearyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
9, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 1.0 Stearyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) =
1.7, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 0.8 Isobonyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
2.0, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp
² ) = 1.1 Isobonyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.8, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp
² ) = 0.9 Isobonyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.
4, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 1.5 Isobonyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
9, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp ² )
= 1.0 Isobonyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) =
1.7, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 0.8 t-butyl methacrylate (8.3) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
2.0, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δp)
² ) = 1.0 t-butyl methacrylate (8.3) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.8, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δp)
² ) = 0.8 t-butyl methacrylate (8.3) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.
4, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δp ² )
= 1.4 t-butyl methacrylate (8.3) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
9, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δp ² )
= 0.9 t-butyl methacrylate (8.3) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ −δd) =
1.7, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δp)
² ) = 0.7 A combination of the above copolymer resin with n-heptane, n-octane, nonane, decane, dodecane, cyclohexane or the like is also preferable.

When perchloroethylene (δd = 9.3) is used as a dispersion medium, preferred copolymer resins include:
For example, there is the following. Ethylene (8.1) -vinyl acetate (9.4) copolymer resin, Δ (δp ¹ −δd) = 1.2, Δ (δp ² −δd) =
0.1, Δ (δp ¹ −δp ² ) = 1.3 Ethylene (8.1) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.2, Δ (δp ² −δ
d) = 0.4, Δ (δp ¹ −δp ² ) = 1.6 Ethylene (8.1) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.2, Δ (Δp ² −δ
d) = 0.1, Δ (δp ¹ −δp ² ) = 1.1 Styrene (9.1) -isoprene (8.15) copolymer resin, Δ (δp ¹ −δd) = 1.15, Δ ( δp ² -δd)
= 0.2, Δ (δp ¹ −δp ² ) = 0.95 Lauryl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² ) =
1.1 Lauryl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp ² )
= 0.9 lauryl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.5 lauryl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 1.0 lauryl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp ² )
= 0.8 stearyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² )
= 1.1 Stearyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 0.9 Stearyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.5 Stearyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 1.0 Stearyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) =
1.1, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp)
² ) = 0.8 Isobonyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² )
= 1.1 Isobonyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 0.9 Isobonyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.5 Isobonyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 1.0 Isobonyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) =
1.1, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp)
² ) = 0.8 t-butyl methacrylate (8.3) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.0, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² )
= 1.0 t-butyl methacrylate (8.3) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.0, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 0.8 t-butyl methacrylate (8.3) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
0, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.4 t-butyl methacrylate (8.3) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
0, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 0.9 t-butyl methacrylate (8.3) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ −δd) =
1.0, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp)
² ) = 0.7 Preferable copolymer resins when trichloroethane (δd = 9.9) is used as the dispersion medium include, for example, the following. n-propyl methacrylate (8.8) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 0.9 n-propyl methacrylate (8.8) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0.6, Δ (δp ¹ −δp)
² ) = 0.5 n-butyl methacrylate (8.7) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
2, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp ² )
= 1.0 n-butyl methacrylate (8.7) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
2, Δ (δp ² −δd) = 0.7, Δ (δp ¹ −δp ² )
= 0.5 n-butyl methacrylate (8.7) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.2, Δ (δp ² −δd) = 0.6, Δ (δp ¹ −δp)
² ) = 0.6 n-hexyl methacrylate (8.6) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 1.1 n-hexyl methacrylate (8.6) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.7, Δ (δp ¹ −δp)
² ) = 0.6 n-hexyl methacrylate (8.6) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.6, Δ (δp ¹ −δp)
² ) = 0.7 n-hexyl methacrylate (8.6) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.8, Δ (δp ¹ −δp
² ) = 0.5 [Method for producing matte wet type developer] The method for producing the wet type developer of the present invention includes a method utilizing the difference in SP value between a solvent and an electrically insulating dispersion medium, and a method using such a SP value. There is a method that does not use the difference of

When the difference in SP value between the solvent and the electrically insulating dispersion medium is not used, a powder or pellet of the copolymer resin is used as it is, or a varnish in which the copolymer resin is dispersed or dissolved is used.
What is necessary is just to mix with an electrically insulating dispersion medium in the presence of a mat pigment. To make the mat pigment coexist in the mixing place, the copolymer resin or its varnish and the powder of the mat pigment may be simultaneously added to the electric insulating dispersion medium, or the mat pigment may be added to the electric insulating dispersion medium. The copolymer resin or its varnish may be added after the powder is added first. After dispersing the mat pigment in the electrically insulating dispersion medium, the solvent of the varnish is removed by an evaporator or the like as necessary. However, if the solvent of the varnish does not adversely affect the physical properties of the toner even if it remains in the wet developer, the solvent of the varnish need not be removed.

When the difference in SP value between the solvent and the electrically insulating dispersion medium is used, (1) the copolymer resin is dissolved in the solvent or the varnish of the copolymer resin is mixed with the solvent to obtain (2) The solution of the copolymer resin thus obtained may be mixed with an electrically insulating dispersion medium in the presence of a mat pigment, and then (3) the solvent may be removed. The copolymer resin particles are precipitated (granulated) in at least one of the step (2) of mixing the electrically insulating dispersion medium or the step (3) of removing the solvent.

First, in the step (1), the copolymer resin is dissolved using a suitable solvent. It is preferable that the copolymer resin is completely dissolved in the solution, but it may be in a swollen state or a partial homopolymer chain present in the copolymer resin even if it is in an insoluble state. Should be well dispersed. Further, the solvent is preferably one that can dissolve and swell the copolymer resin at room temperature (25 ° C.), or can disperse a partial homopolymer chain well. Furthermore, the solvent must be insoluble or poorly soluble in the matte pigment.

The dispersant is added to the copolymer resin solution in an amount of 0.3 to 0.3.
If it is contained in the range of 0.5% by weight, the state of dispersion of the resin can be improved. The amount of the copolymer resin dissolved in the solvent is arbitrary, but if the proportion of the resin is too high, the resin particles may come into contact with each other in the granulation step and form a gel-like mass, and thus usually 1 to 80 wt. %, A solution containing a copolymer resin in a ratio of 5% is prepared.
Prepare a 溶液 10% by weight dilute solution.

Next, in the step (2) of mixing the electrically insulating dispersion medium, the solution prepared in the step (1) and the electrically insulating dispersion medium are mixed together in the presence of a mat pigment such as silica fine particles. Mix to precipitate copolymer resin particles.

For example, when a solution of a styrene-isoprene copolymer resin dissolved in toluene at a ratio of 10% by weight of the toluene weight is mixed with n-hexane, the mixture becomes cloudy, and precipitation of the styrene-isoprene copolymer resin particles is clearly observed. it can. Further, when the above resin solution is mixed with n-hexane in the presence of silica fine particles as a mat pigment, it becomes difficult to confirm white turbidity because the silica fine particles are dispersed, but the resin particles containing the pigment become glass bottles. It can be observed that it adheres to the wall surface.

In order to allow a mat pigment such as silica fine particles to coexist at the time of mixing, the mat pigment powder may be added to either the resin solution or the electrically insulating dispersion medium. When the resin solution and the dispersion medium are mixed in the coexistence of the mat pigment, the resin molecular chains that have been dissolved, swelled, or dispersed at the molecular level in the solution are filled with an electrically insulating dispersion medium that is a poor solvent. Will be added to the environment. As a result, the molecular chain of the copolymer resin is adsorbed on the surface of the mat pigment via the first monomer unit having a higher affinity for the mat pigment than for the dispersion medium, and wraps the mat pigment particles. Entangling, resin particles are formed.

As described above, the charge control agent such as metal soap and lecithin may be added to raw materials such as a copolymer resin or a mat pigment at any stage of the production process, or may be added to a material other than the raw materials, for example, a solvent. Or may be added to the intermediate product after granulation or after removing the solvent. Preferably, it is preferably added in advance to either the resin solution or the electrically insulating dispersion medium so that granulation can be performed in the presence of both the mat pigment and the charge control agent.

In the step (3), the solvent is removed from the liquid mixture containing the copolymer resin particles, the dispersion medium and the good solvent. From the viewpoint of granulation properties, it is preferable to remove the solvent by a method such as decantation or evaporation. In addition, in order to adjust the particle size of the resin particles, ball mill, attritor, sand grinder,
Fine particles may be further formed using a Keddy mill, a three-roll mill, or the like.

However, since the gloss of the matte pigment is greatly affected by the particle size of the pigment, it is necessary to set a disperser and dispersion conditions so as to obtain the required gloss.

Thus, a wet developer in which the copolymer resin particles containing the mat pigment are dispersed in the electrically insulating dispersion medium is obtained. The core portion of the copolymer resin particles is mainly formed by the mat pigment and the portion of the first monomer unit adsorbed on the surface of the mat pigment, and is insoluble in the dispersion medium. An outer edge portion rich in the second monomer unit having a high affinity for the medium is formed. Therefore, even if a large amount of mat pigment is contained in the dispersion medium, contact between the mat pigments is avoided, gelation, macroscopic aggregation, precipitation, etc. do not occur, and the dispersion stability is excellent. The content ratio of the copolymer resin particles in the wet developer is usually 0.01 to 80% by weight, preferably 0.1 to 50% by weight.
And

(2) Method for Producing Highly Designed Articles Using Matte Wet Developer The matte wet particles of the present invention have suitably dispersed matt toner particles having appropriate chargeability. Therefore, by using the matte wet developer of the present invention, it is possible to apply a matte image to the surface of various sheet-like or three-dimensional printing materials by a printing method using an electrostatic action, A highly designed article is obtained.

In particular, the matte wet developer of the present invention is suitable for an on-demand type printing system such as electrostatic recording and electrostatic transfer among electrostatic printing systems, and is capable of forming an image having a matte feeling. Printing can be performed easily and quickly.

When the matte wet developer of the present invention is used, an image having a matte feeling can be formed by an electrostatic printing method regardless of whether or not the base of the printing material has a gloss. In particular, even when the material of the base cannot be freely selected, such as when attaching a matte image to furniture or building interior materials, if the matte wet developer of the present invention is used, the matte is formed by an electrostatic method. An image having a feeling can be formed.

[0096] In order to apply a matte image to furniture, building interior materials, soft packaging materials, and high-quality printed materials using the matte wet developer of the present invention, for example, the following may be performed. First, the matte wet developer of the present invention, furniture, building interior materials,
Prepare a packaging material such as a soft packaging material, a high-quality printed matter printed on paper or film, or a raw material thereof. Here, the raw material of the furniture or the building interior material means a material created in the furniture or the building interior material, for example, a preform,
It corresponds to a roughly formed body, a part, a plate material and the like. These raw materials may be dyed uniformly, or may have patterns formed on demand or by a normal printing method.

Next, an image is output on the surface of furniture, building interior materials, soft wrapping material or high-quality printed material, or a raw material by a printing method using a matte wet developer and utilizing an electrostatic action. . Examples of a printing method using an electrostatic action include an electrostatic plotter, an electrophotographic method, and electrostatic gravure printing. The output image is
The image may be a uniform solid image, an artificial pattern such as an array of characters, symbols, or figures, or a pattern imitating a natural object such as a grain of wood, a grain of stone, or a cloud.

Among the printing methods utilizing the electrostatic action, there are on-demand type printing methods such as electrostatic recording using an electrostatic plotter or the like and electrostatic transfer using an electrophotographic printer. In the case of such an on-demand method, a designed image is synthesized by digital processing, and can be immediately output to the surface of a printing medium without going through a plate making process.

After forming a matte image on the surface of furniture, architectural interior materials, soft wrapping materials, high-quality printed materials, or raw materials, post-processing is performed as necessary to form articles having high design properties. can do. The post-processing includes, for example, performing surface painting using a melamine paint or the like, or performing embossing. Further, when an image having a matte feeling is attached to a raw material of a foamed product such as a foamed wallpaper or a foamed floor material, the foaming process is continuously performed.

A preferred embodiment of the method for producing a highly-designed article will be described below. In the method shown below, the surface of a printing material, that is, a printed material having a uniform or patterned color image, is subjected to electrostatic recording using the above-described matte wet type developer to form a uniform pattern having a matte feeling. Alternatively, a predetermined pattern is output. According to this method, it is possible to produce a printed matter having a very high designability, having a color image and a surface pattern having a matte feeling.

Here, according to the electrostatic recording method, an electrostatic latent image is directly formed on the surface of a printing material, and the printing material is exposed to a wet developer to develop the electrostatic latent image. On the other hand, according to the electrostatic transfer method, an electrostatic latent image is formed on the surface of a dielectric material that is not a printing material, and the dielectric material is exposed to a wet developer to develop the electrostatic latent image. The pattern of the matte pigment formed thereon is transferred directly or indirectly to the surface of the printing material.
In electrostatic transfer, a toner pattern on a dielectric can be directly transferred onto a transfer target by electrostatic force. Alternatively, the toner pattern on the dielectric is once transferred onto the intermediate receiver by electrostatic force, and the toner pattern on the intermediate receiver is transferred onto the transfer receiver by a method such as thermal transfer. It may be transferred indirectly on the top. Examples of the dielectric include dielectrics such as alpet (polyethylene terephthalate vapor-deposited with aluminum) and electrostatic recording paper, and electrophotographic photosensitive members.

FIGS. 1 to 8 show a pseudo tile mat print, that is, a mat print having an appearance surface such as a tile by using electrostatic recording and electrostatic transfer techniques. This is an explanation of the process.

FIG. 1 is a partial plan view of an example of a printing material, and FIG. 2 is a schematic cross-sectional view taken along line AA. As shown in FIG. 2, the printing material 1 is provided with a dielectric layer 3 on one surface side of a support 2.

The support 2 may be formed by using a material conventionally used for furniture, building interior materials, soft wrapping materials and high-quality printed products. As the support 2, for example, paper, woven fabric, knitted fabric, felt, nonwoven fabric, and the like can be used.

The dielectric layer 3 is formed of a resin or a resin composition having an excellent chargeability in order to impart a proper chargeability to the surface of the print. This dielectric layer 3 may be formed using a material conventionally used when performing electrostatic recording. Preferred materials for the dielectric layer include acrylic resin, styrene resin, polyester, polyolefin, polyamide, polyether, polyimide, polyamideimide, polyetherester, poly-p-phenylene sulfide, polyvinyl chloride, fluorine resin, and polycarbonate resin. Etc. can be exemplified. In addition, it is preferable that the back surface of the printing of the dielectric layer 3 or the support 2 is subjected to a conductive treatment from the viewpoint of the charging property at the time of printing.

The printing material 1 is prepared, and an electrostatic latent image 4 is formed on the surface of the dielectric layer 3. In FIG.
Since the joint portion of the tile pattern is intended to be a color image, the electrostatic latent image 4 in which the charged portion has a lattice pattern is formed. Next, when the surface of the dielectric layer 3 having the electrostatic latent image 4 is developed by exposing it to a color wet type developer, the copolymer resin particles dispersed in the developer adhere to the charged portion of the electrostatic latent image 4. I do. As a result, a color image 6 is formed on the surface of the dielectric layer 3 as shown in FIGS. In this way, an intermediate product 5 with a color image is obtained.

Next, as shown in FIGS. 6, 7 and 8,
Electrostatic transfer is performed on the surface of the dielectric layer 3 of the intermediate product 5 using a matte wet developer in which toner particles including a mat pigment are dispersed, and the mat toner is adhered in a predetermined pattern. In FIG. 6, since the joint portion of the tile pattern is intended to be a mat image, the matt toner attachment portion 8 is formed in a lattice pattern. In this manner, a high-design product 7 having the color image 6 and the matted toner adhering portion 8 is obtained.

The color wet type developer used herein is composed of a copolymer resin composed of at least two types of monomer units including a first monomer unit and a second monomer unit in an electrically insulating dispersion medium. And a wet developer in which copolymer resin particles containing color pigments such as yellow, magenta, cyan, and black are dispersed,
(1) The electric insulating dispersion medium and the copolymer resin are
(I) The difference Δ (δp between the solubility parameter value δp ^{1 of} the homopolymer composed only of the first monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium.
¹⁻ δd) is 1.0 or more, and (ii) the difference between the solubility parameter value δp ^{2 of} the homopolymer composed only of the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium. Δ (δp ² −δd) is 1.0
And (iii) the difference Δ (δp ¹ −δp ² ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
Is 0.5 or more, and (2)
The copolymer resin particles are composed of a core portion insoluble in the dispersion medium and an outer edge portion surrounding the core portion, which dissolves or swells in the dispersion medium.

This color wet developer can be produced by the same method as the matte wet developer of the present invention. That is, a color wet developer can be obtained by mixing a good solvent solution or varnish of a copolymer resin with an electrically insulating dispersion medium in the presence of a color pigment and then removing the solvent as needed. The solvent for dissolving the copolymer resin, the varnish of the copolymer resin, the electrically insulating dispersion medium, and the like may be selected from those usable for producing a matte wet developer. However, in a specific combination of the matte wet type developer and the color wet type developer, the electrically insulating dispersion medium and the copolymer resin used in each of the two developers may be the same or different.

In the above method, development is first performed using a color wet developer, and then development is performed using a matte wet developer. You may. In the above method, electrostatic recording is performed using a color wet developer, and electrostatic transfer is performed using a matte wet developer. However, electrostatic transfer is performed using a matte wet developer, and color wet Electrostatic recording may be performed using a developer. Of course, a color image having a unique design may be formed by alternately developing a matte wet developer and a color wet developer such as yellow, magenta, cyan, and black.

Further, in the present invention, a brilliant wet developer may be used in place of the color wet developer. Printing with an agent may be combined. Instead of the matte pigment, the glittery wet developer is composed of glittering pigments, such as pearl pigments, metal powders, pieces of deposited plastic film, and different refractive indices.
It can be produced by the same method as the matte wet type developer of the present invention using at least one kind of resin layer and the like.

Next, the printed matter according to the present invention will be described. The printed matter according to the present invention has a mat print layer printed using the above-mentioned matte wet type developer, on a printing medium selected from furniture, building interior materials, packaging materials, paper, films, and raw materials thereof. In which at least one layer is provided. Such a printed matter according to the present invention will be described with reference to FIGS.

FIG. 9 shows a mat printing layer 10 on a printing medium 9.
Only the example shown in FIG. The mat print layer 10 is a print layer using the above-mentioned matte wet type developer. Further, it is preferable that the printing method is a printing method using an on-demand type printing method by an electrostatic action such as electrostatic recording or electrostatic transfer. Further, the mat print layer 10 may be a solid image, or may have a predetermined pattern printed thereon.

The printed matter of the present invention is not limited to the one in which only the mat printing layer 10 is printed on the printing medium as shown in FIG. 9, and for example, at least one sheet as shown in FIGS. Any layer may be used as long as it is printed with a mat printing layer using the matte wet developer described above. FIG.
This shows an example in which a color printing layer 11 is printed on a printing medium 9 and a mat printing layer 10 is further printed thereon. Here, the color printing layer is not limited to the one printed by the on-demand type printing method by the electrostatic action using the color wet developer as described above, and for example, an original plate such as gravure printing is formed. The printing layer may be a printing layer printed by a printing method that is performed by using a printing method.

FIG. 11 shows the color printing layer 1 on the printing medium 9.
No. 1 is printed, a glitter print layer 12 is printed thereon, and finally a mat print layer 10 is printed. This brilliant printing layer 12 is not limited to the one printed by the on-demand type printing method like the color printing layer 11, but is a printing method using an original plate such as ordinary gravure printing. Is also good.

FIGS. 12 to 16 show examples in which the respective print layers of the printed body shown in FIG. 11 are replaced. FIG. 12 shows a glitter print layer 12, a color print layer 11, FIG. 13 shows a color printing layer 11, a mat printing layer 10, and a glittering printing layer 12, and FIG. 14 shows a mat printing layer 10, a color printing layer 11. 15 is the order of the glitter print layer 12, FIG. 15 is the order of the mat print layer 10, the glitter print layer 12, and the color print layer 11,
FIG. 16 shows an example in which the glitter print layer 12, the mat print layer 10, and the color print layer 11 are printed in this order. In the present invention, two or more color print layers may be formed, two or more glitter print layers may be formed, and two or more mat print layers may be formed. Or a combination of these. At this time, as described above, with respect to the mat print layer, at least one layer needs to be a print layer using the above-described matte wet developer, but the other print layers are
The printing layer may be an on-demand printing layer using a wet developer or a printing layer printed by gravure printing using an original plate.

[0117]

EXAMPLES Hereinafter, the wet developer according to the present invention will be described in more detail with reference to Examples.

Example 1 A wet developer 1 having the following composition was produced. First, the respective materials other than the dispersion medium for dilution were mixed, and the mixture was placed in a mixing container together with the glass beads for dispersion, and mixed with a disperser (RC-5000, manufactured by Red Devil Co.).
After dispersion for a time, the glass beads for dispersion were removed to obtain a master toner. Further, 60 parts by weight of the obtained master toner was diluted with 660 parts by weight of Isopar for dilution, and the total amount was adjusted to 720 g, whereby a matte wet developer 1 was obtained. The toner particles were positively charged. <Composition of Wet Developer 1> A varnish of 2-ethylhexyl methacrylate (EHMA) / dimethylaminoethyl methacrylate (DMAEMA) copolymer resin (first monomer unit: DMAEMA (δ)
p ¹ = 9.1), second monomer unit: EHMA (δp ² =
7.7), solid content: 40% by weight, dispersion medium: brand name Isopar G, weight ratio: EHMA / DMAEMA = 80/2
0, weight average molecular weight: 170,000): 10.0 parts by weight Matte pigment Silica pigment (Mizukasil P-526, average particle diameter 3.0 μm, manufactured by Mizusawa Chemical Industry Co., Ltd.): 4.0 parts by weight Control agent Zirconium naphthenate (Nikka Naphtex Zr, manufactured by Nippon Kagaku Sangyo): 6.0 parts by weight Dispersion medium for master toner Product name Isopar G (δd
= 7.3, manufactured by Exxon): 40.0 parts by weight (subtotal: 6)
0.0 parts by weight) Dispersion medium for dilution Trade name: Isopar G (manufactured by Exxon): 660 parts by weight (total: 720 parts by weight) [Example 2] 2-ethylhexyl methacrylate / dimethylaminoethyl methacrylate copolymer resin Varnish,
Equal amount of 2-ethylhexyl methacrylate (EHMA)
/ Varnish of dimethylacrylamide (DMAA) copolymer resin (first monomer unit: DMAA (δp ¹ = 12.
8), the second monomer unit: EHMA (δp ² = 7.
7), solid content: 40% by weight, dispersion medium: trade name: Isopar G, weight ratio: EHMA / DMAA = 80/20, weight average molecular weight: 190,000)
Was carried out in the same manner as in the above to obtain a matte wet type developer 2. The toner particles were positively charged.

Example 3 A varnish of 2-ethylhexyl methacrylate / dimethylaminoethyl methacrylate copolymer resin was mixed with the same amount of 2-ethylhexyl methacrylate (EHMA) / diacetone acrylamide (DAA).
A) Varnish of copolymer resin (first monomer unit: DAAA)
(Δp ¹ = 10.9), second monomer unit: EHMA
(Δp ² = 7.7), solid content: 30% by weight, dispersion medium: Isopar G (trade name), weight ratio: EHMA / DAAA = 90
/ 10, weight average molecular weight: 130,000), except that the matte wet developer 3 was used.
I got The toner particles were positively charged.

Example 4 A varnish of 2-ethylhexyl methacrylate / dimethylaminoethyl methacrylate copolymer resin was mixed with the same amount of 2-ethylhexyl methacrylate (EHMA) / isopropyl acrylamide (IPA).
A) Varnish of copolymer resin (first monomer unit: IPAA)
(Δp ¹ = 10.7), second monomer unit: EHMA
(Δp ² = 7.7), solid content: 30% by weight, dispersion medium: Isopar G (trade name), weight ratio: EHMA / IPAA = 90
/ 10, weight average molecular weight: 90,000), to obtain a matte wet developer 4. The toner particles were positively charged.

Example 5 A matte wet developer 5 was prepared in the same manner as in Example 2 except that the mat pigment was changed to kaolin (trade name: kaolin, average particle size: 3.5 μm, manufactured by Junsei Chemical Co., Ltd.). I got The toner particles were positively charged.

Example 6 A varnish of 2-ethylhexyl methacrylate / dimethylaminoethyl methacrylate copolymer resin was mixed with a varnish of 2-ethylhexyl methacrylate (EHMA) / acrylic acid (AA) copolymer resin (first monomer). Unit: AA (δp ¹ = 9.4), second monomer unit: EHMA (δp ² = 7.7), solid content: 3
0% by weight, dispersion medium: brand name Isopar G, weight ratio: EH
MA / AA = 70/30, weight average molecular weight: 42,000
0) and the mat pigment was changed to talc (trade name: High Micron G, average particle size 1.3 μm, manufactured by Fuji Talc Co., Ltd.)
And a matte wet developer 6 was obtained in the same manner as in Example 1 except that zirconium naphthenate was replaced with the same amount of lecithin. The toner particles were negatively charged.

Example 7 A matte wet method was carried out in the same manner as in Example 6 except that the mat pigment was changed to talc (trade name: Micro Ace, average particle size: 1.8 μm, manufactured by Nippon Talc Co., Ltd.). Developer 7 was obtained. The toner particles were negatively charged.

Example 8 A matte wet process was performed in the same manner as in Example 6, except that the mat pigment was changed to calcium carbonate (trade name: Nanox, average particle size 1.2 μm, manufactured by Maruo Calcium Co., Ltd.). Developer 8 was obtained. The toner particles were negatively charged.

Example 9 Matte wet development was conducted in the same manner as in Example 6, except that the mat pigment was changed to silica (trade name: Nip Seal, average particle size: 2 to 3 μm, manufactured by Nippon Silica Co., Ltd.). Agent 9 was obtained. The toner particles were negatively charged.

Comparative Example 1 A varnish of 2-ethylhexyl methacrylate / dimethylaminoethyl methacrylate copolymer resin was used as the copolymer resin, and a varnish of the same amount of 2-ethylhexyl methacrylate (EHMA) monopolymer resin (monomer unit: EHMA) (Δp ² = 7.7), solid content: 4
0% by weight, dispersion medium: brand name Isopar G, weight ratio: EH
MA = 100%, weight average molecular weight: 100,000) was carried out in the same manner as in Example 1 to obtain a comparative developer 1 of a matte pigment. No adhesion to the electrode plate was observed.

COMPARATIVE EXAMPLE 2 A mat pigment was prepared using titanium oxide (trade name: titanium oxide R-960, average particle size 0.4 μm).
m, manufactured by DuPont) to obtain a comparative developer 2 in the same manner as in Example 1. The toner particles were positively charged.

[Evaluation] (1) Formation of an image having a matte feeling A voltage of -6 KV was applied to the surface of the electrostatic recording paper by a scorotron to partially charge the surface potential to -150 V. Forming an electrostatic latent image, and then
Vat development was performed using each of the wet developers obtained in Steps (1) to (4). As a result, a pattern having a matte feeling was successfully output.

In Examples 5 to 8 and Comparative Example 1, a binary pattern in which a voltage of +6 KV was applied to the surface of the electrostatic recording paper to partially charge the surface potential to +150 V in the same manner as described above. Was formed and bat developed.
As a result, in Examples 5 to 8, a pattern having a matte feeling was successfully output. However, in Comparative Example 1, the fixability of the image was poor, and the image on the electrostatic recording paper flowed.

(2) Evaluation method of charge amount The charge amount of the copolymer resin particles was measured by the following method.
A wet developer is filled between a brass electrode plate having an interval of 1.0 cm, a length of 5.0 cm, and a width of 4.5 cm, and a high voltage generator (type 237 manufactured by KEITHLEY) is used to fill the space between the two electrodes.
A voltage of 00 V was applied, and a current value was measured over time from the start of energization until a lapse of 60 seconds. Based on the measured value, first, the current value (I ₆₀ ) after the lapse of 60 seconds from the initial current amount (I ₀ ) at the start of energization is integrated, and 6 hours after the start of energization.
The initial total charge amount Q ₀ spent until 0 seconds had elapsed was calculated. Next, based on the current value 60 seconds after the start of energization,
The amount of charge Q ₆₀ spent in 60 seconds in the steady state was calculated. Then, to calculate the total charge Q _t of the copolymer resin particles by calculating the difference between the two charge amount. The equation for the above calculation is expressed as follows.

[0131]

Equation 3] _{Q t = Q 0 -Q 60 =} Q 0 -I 60 × 60 seconds then removed electrode plate wet developer is adhered from the current value measuring cell, dried, and the amount of toner deposited on the electrode plate (M) was measured. Based on the adhesion amount (M) and the total charge amount Q _t, it was calculated charge amount of the toner specific charge ie per toner _{1g Q t / M (μc /} g). Table 1 shows the measurement results.

[0132]

[Table 1] ・ EHMA: 2-ethylhexyl methacrylate ・ DMAEMA: dimethylaminoethyl methacrylate ・ DMAA: dimethylacrylamide ・ DAAA: diacetone acrylamide ・ IPAA: isopropylacrylamide ・ AA: acrylic acid

[0133]

[Table 2]

[0134]

According to the present invention, there is provided a wet developer containing a mat pigment and excellently dispersing toner particles having excellent chargeability. By using such a wet developer, it is possible to apply various patterns or uniform images to various printed materials on a glossy printed material by a method using an electrostatic action such as electrostatic recording, electrostatic transfer, and electrostatic printing. An image with a matte feeling can be attached. In particular, according to an on-demand type technique such as electrostatic recording or electrostatic transfer, a printing plate is not required, and an image having an arbitrary matte feeling can be formed quickly and easily.

The matte wet type developer of the present invention can form an image having a matte feeling in an arbitrary pattern even if the base color has a glossiness, and therefore the material is limited, such as furniture and building interior materials. It is suitable for forming a matte image on a non-printed body. In addition, since it can be used for on-demand type printing, it is necessary to produce prototypes of high-design furniture and building interior materials, create samples for their presentation, and launch small-volume small-volume products such as packaging and high-quality printed materials. Can respond flexibly to

[Brief description of the drawings]

FIG. 1 is a partial plan view showing an example of a printing material.

2 is a diagram schematically illustrating a cross section taken along the line AA of the printing material of FIG. 1;

FIG. 3 is a plan view showing a state in which an electrostatic latent image is formed on the surface of the printing material.

FIG. 4 is a partial plan view showing an intermediate product formed by developing an electrostatic latent image on the surface of a printing material with a matte wet developer.

FIG. 5 is a diagram schematically showing a BB cross section of the intermediate product of FIG. 4;

FIG. 6 is a partial plan view showing a high-design product provided with a color image and a mat image attaching portion.

FIG. 7 is a diagram schematically showing a CC section of the high-design product of FIG. 6;

8 is a diagram schematically showing a DD section of the high-design product of FIG. 6;

FIG. 9 is an explanatory diagram showing an example of a printed matter of the present invention.

FIG. 10 is an explanatory diagram showing another example of the printed matter of the present invention.

FIG. 11 is an explanatory view showing another example of the printed matter of the present invention.

FIG. 12 is an explanatory view showing another example of the printed matter of the present invention.

FIG. 13 is an explanatory diagram showing another example of the printed matter of the present invention.

FIG. 14 is an explanatory diagram showing another example of the printed matter of the present invention.

FIG. 15 is an explanatory diagram showing another example of the printed matter of the present invention.

FIG. 16 is an explanatory diagram showing another example of the printed matter of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Printing raw material 2 ... Support 3 ... Dielectric layer 4 ... Electrostatic latent image 5 ... Intermediate product 6 ... Color image 7 ... Highly designed product 8 ... Adhesion part of mat image 9 ... Printed object 10 ... Mat printing layer 11 ... Color printing layer 12 ... Glitter printing layer

Claims (14)

[Claims] 1. A matte wet developer comprising resin particles containing a mat pigment dispersed in an electrically insulating dispersion medium. 2. An average particle size of the mat pigment is 0.5 to 2.
The matte wet developer according to claim 1, wherein the developer is within a range of 20 µm. 3. The electrically insulating dispersion medium, wherein the resin particles are copolymer resin particles composed of a copolymer resin composed of at least two types of monomer units including at least a first monomer unit and a second monomer unit. And the copolymer resin, (i) a difference Δ (δp ¹⁾ between the solubility parameter value δp ^{1 of} the homopolymer composed of only the first monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium. −δ
d) is 1.0 or more, and (ii) the difference Δ () between the solubility parameter value δp ^{2 of} the homopolymer composed of only the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium. δp ² −δd) is 1.0 or less, and (iii) the difference Δ (δp ¹ −δp ² ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers is 0.
A core portion insoluble in the electrically insulating dispersion medium, and an outer edge portion surrounding the core portion that dissolves or swells in the electrically insulating dispersion medium. The matte wet developer according to claim 1 or 2, wherein the developer comprises: 4. The method according to claim 1, wherein the first monomer unit is a monomer unit having a basic group, and the second monomer unit is 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, and 4. The matte wet developer according to claim 3, wherein a copolymer resin which is a monomer unit derived from at least one monomer selected from the group consisting of ethylene is used. 5. The monomer unit having a basic group,
It is a monomer unit derived from at least one monomer selected from the group consisting of dimethylaminoethyl acrylate, dimethylacrylamide acrylate, diacetone acrylamide, isopropylacrylamide, dimethylaminoethyl methacrylate, and dimethylacrylamide methacrylate. The matte wet type developer according to claim 4, characterized in that: 6. The matte wet developer according to claim 4, wherein the developer contains a metal soap as a charge control agent and the copolymer resin particles are positively charged. 7. The first monomer unit is a monomer unit having an acidic group, and the second monomer unit is 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, and ethylene. The matte wet developer according to claim 3, wherein a copolymer resin which is a monomer unit derived from at least one kind of monomer selected from the group consisting of: 8. The monomer unit having an acidic group is a monomer unit derived from at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and vinyl acetate. A matte wet developer as described in the above. 9. The matte wet developer according to claim 7, wherein lecithin is contained as a charge control agent, and the copolymer resin particles are negatively charged. 10. A printing medium selected from furniture, architectural interior materials, packaging materials, paper, films, and raw materials thereof, and a printing medium according to any one of claims 1 to 9. A first step of preparing a matte wet developer, and performing electrostatic recording or electrostatic transfer using the matte wet developer to form resin particles containing a matte pigment on the surface of the printing medium. A method for producing a highly-designed article, comprising at least a second step of adhering. 11. The method according to claim 10, wherein post-processing is performed after the second step to enhance the design. 12. The printing apparatus according to claim 1, wherein the printing medium is selected from furniture, building interior materials, packaging materials, paper, films, and raw materials thereof. Printed matter having at least one mat printing layer printed by using the matte wet developer according to (1). 13. The post-processing after forming the outermost layer of each layer on the printing medium.
Printed matter described. 14. The post-processing is embossing, and the raw material is a vinyl chloride raw material.
Printed matter described.